EP0879269A1 - Hot-melt adhesives with copolymer base having epoxy functions - Google Patents

Hot-melt adhesives with copolymer base having epoxy functions

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Publication number
EP0879269A1
EP0879269A1 EP97947087A EP97947087A EP0879269A1 EP 0879269 A1 EP0879269 A1 EP 0879269A1 EP 97947087 A EP97947087 A EP 97947087A EP 97947087 A EP97947087 A EP 97947087A EP 0879269 A1 EP0879269 A1 EP 0879269A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
meth
acrylate
ethylene
hot
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97947087A
Other languages
German (de)
French (fr)
Inventor
Jean Lebez
Jean-Michel Pierrot
Eric Radigon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0879269A1 publication Critical patent/EP0879269A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C09J123/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to a hot-melt adhesive based on copolymers with epoxy functions and more particularly those based on a copolymer of ethylene and of a monomer with an epoxy function, this monomer being capable of being grafted or copolymerized.
  • Hot melt adhesives are thermoplastic materials which are solid at room temperature and which, on heating, become viscous liquids. These viscous liquids are applied to a first substrate and then covered with a second surface. By cooling, an adhesion is obtained between the substrate and the second surface.
  • the open time is the time during which the adhesive which has been applied to a substrate which is at room temperature remains tacky, that is to say during which the second surface can be applied and by cooling obtaining adhesion between the substrate and the second surface.
  • the setting time is the time necessary for the adhesion between the substrate and the second surface after their junction to reach a value sufficient to maintain their intimate junction.
  • the adhesion can still change over time if the adhesive contains crosslinkable functions, for example, isocyanate functions crosslinkable at ambient humidity.
  • crosslinkable functions for example, isocyanate functions crosslinkable at ambient humidity.
  • hotmelt adhesives are also characterized by their shear strength as a function of temperature (SAFT test: SHEAR ADHESION FAILURE TEMPERATURE).
  • thermoplastic polymer - responsible for good mechanical and thermal properties
  • tackifying resin which is involved in adhesion, hot tackiness, fluidity and wettability.
  • a number of additives such as waxes, stabilizers, fillers are most often added thereto. Waxes (for example paraffins) make it possible to adjust the fluidity, the open time and the setting time.
  • the most widely used thermoplastic polymers are ethylene-vinyl acetate copolymers (hereinafter called EVA), ethylene- (meth) alkyl acrylate, poly- ⁇ -atactic olefin (APAO), thermoplastic rubber, and others.
  • Tackifying resins mainly belong to three main families: rosins (and their derivatives), terpene resins and petroleum-based resins (aliphatic, aromatic, and others).
  • EP 547,798, US 4,874,804 and US 5,242,980 describe such hot-melt adhesives based on ethylene-n-butyl acrylate copolymers.
  • EP 380 379 and EP 600 767 describe hot-melt adhesives crosslinkable with humidity based on a prepolymer with free isocyanate functions.
  • US 5,242,980 describes hot-melt crosslinkable adhesives consisting of a mixture of an ethylene copolymer having carboxylic acid functions and of a crosslinker having at least two epoxide functions such as for example the diglycidyl ether of bisphenol A. The crosslinker must be encapsulated to avoid premature crosslinking during the heating of the adhesive to apply it to the substrate.
  • adhesives having improved properties compared to adhesives based on ethylene- (meth) acrylate copolymers can be obtained by using ethylene copolymers and comprising epoxide units, in particular for the same temperature the peel strength on aluminum for an adhesive based on an ethylene-butyl acrylate-glycidyl methacrylate copolymer is higher than that of an adhesive based on an ethylene-butyl acrylate copolymer.
  • the present invention relates to a hot-melt adhesive based on a copolymer (A) comprising patterns:
  • vinyl esters mention may be made of vinyl esters of saturated carboxylic acids having from 2 to 6 carbon atoms such as vinyl acetate or vinyl propionate.
  • alkyl (meth) acrylates of those whose alkyl group has from 1 to 10 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) n-butyl acrylate, isobutyl (meth) acrylate and 2-ethyl-hexyl (meth) acrylate.
  • n-butyl acrylate is used.
  • Examples of unsaturated epoxides which can be used as constituents of polymer (A) are in particular: - aliphatic glycidyl esters and ethers such as allylglycidylether, vinylglycidylether, glycidyl maleate and itaconate, acrylate and methacrylate glycidyle, and, - alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidylether, cyclohexene-4,5-diglycidylcarvboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis - bicyclo (2,2, 1) -5-heptene-2,3-diglycidyl dicarbo-xylate.
  • the unsaturated epoxide may be copolymerized with ethylene and the other
  • glycidyl methacrylate is used.
  • the amount of unsaturated epoxide can represent up to 10% by weight of the copolymer (A) advantageously 0.1 to 8% and preferably 0.5 to 5% [the percentages and the parts in the present text are by weight except otherwise indicated].
  • the amount of comonomer can represent 0 to 50% of the copolymer (A) and preferably 25 to 40%.
  • the melt index (or Melt Index MI) can be arbitrary provided that a hot-melt adhesive can be formulated and that the adhesive thus formulated has a measured BROOKFIELD viscosity (at 170 ° C. under the following conditions: Needle 27 at 10 turns / minute according to ASTM D 3236) between 1,000 and 10,000 mPa.s and preferably between 2,000 and 8,000.
  • it can be between 0, 1 and 1,500, preferably between 50 and 900 (g / 10 minutes at 190 ° C under 2.1 6 kg ASTM D 1 238).
  • the softening point of (A), also called ball-ring temperature, and measured according to standard ASTM E28 can be between 60 and 110 ° C. and advantageously between 70 and 90 ° C.
  • the copolymer (A) can be a mixture of a polymer (B) which is a copolymer of ethylene and of at least one monomer chosen from vinyl esters and (meth) alkyl acrylates and a polymer (A1) which is a copolymer of
  • the vinyl esters and the alkyl (meth) acrylates can be chosen from the monomers already mentioned above. These monomers can be the same in the polymers (AU and (B).
  • the polymers (AU and (B) may be any provided that the contents of epoxide and MI are advantageously within the ranges mentioned for (A).
  • the polymers (B) and the copolymers (A) in which the epoxide is not grafted can be produced by radical polymerization between 500 and 2800 bars in the presence of a free radical initiator such as a peroxide.
  • copolymers (A) in which the epoxide is grafted they can be prepared, for example, starting from a copolymer of ethylene and optionally a monomer chosen from vinyl esters and (meth) acrylates d alkyl which is brought into contact with the unsaturated epoxide in the presence of an initiator such as a peroxide. This can be done in the molten state or in a solvent.
  • the copolymer (A) is a copolymer of ethylene, of an alkyl (meth) acrylate in which the alkyl group has from 1 to 4 carbon atoms and of glycidyl methacrylate comprising 25 to 35% of (meth ) acrylate and 0.8 to 5% epoxide and having a Melt Index between 1 80 and 250.
  • the alkyl (meth) acrylate is n-butyl acrylate.
  • the adhesives of the invention can also contain one or more tackifying resins, waxes, plasticizers, fillers and stabilizers.
  • Suitable tackifying resins are, for example, rosin, rosin esters, hydrogenated rosin, polyterpenes and derivatives, aromatic or aliphatic petroleum resins, hydrogenated cyclic resins. These resins typically have a ring bead temperature between 25 ° C and 180 ° C and preferably between 50 ° C and 135 ° C.
  • the amount of tackifying resin can be from 50 to 180 parts per 100 parts of copolymer (A) and preferably 100 to 150 parts.
  • the waxes can be recovered during the refining of petroleum fractions. These are, for example, waxes consisting essentially of paraffinic hydrocarbons and containing sufficient quantities of branched, cyclic and aromatic hydrocarbons to be much less crystalline than paraffins. It is also possible to use synthetic waxes such as FISCHER TROPSCH waxes.
  • the paraffin waxes used in the adhesives of the invention have a melting temperature above 50 ° C and preferably between 60 ° C and 70 ° C.
  • the amount of wax can be between 30 and 80 parts per 100 parts of copolymer (A).
  • compositions include 1 20 to 1 30 parts of tackifying resin and 45 to 65 parts of wax per 100 parts of copolymer (A).
  • the plasticizers which can be used in the adhesives of the invention are, for example, aromatic or naphthenic paraffinic mineral oils. They are essentially used to lower the viscosity and to provide tack.
  • the amount of plasticizer can be between 10 and 30 parts per 100 parts of copolymer (A).
  • fillers of silica, alumina, glass, glass beads, calcium carbonates, fibers and metal hydroxides. These fillers must not reduce the tack or the mechanical properties of the adhesive after its application.
  • the quantity of fillers can represent up to 100 parts per 100 parts of copolymer (A).
  • the ring bead temperature of the adhesives of the invention is advantageously between 50 ° C and 100 ° C and preferably 60 ° C and 80 ° C.
  • the cloud point of the adhesives of the invention is less than 180 ° C. and advantageously less than 65 ° C.
  • the cloud point is determined as follows: the glue is heated to 175 ° C. and a drop is deposited on the bulb of an ASTM thermometer, then the temperature at which the cloud appears during cooling is noted.
  • a high cloud point means an adhesive made up of incompatible ingredients and which therefore tends to separate into several phases during the various heating and cooling cycles during its application.
  • the hot-melt adhesives of the invention are prepared by mixing in the molten state at temperatures between 130 ° C. and 200 ° C. until a homogeneous mixture is obtained. The mixing time can be of the order of 30 minutes to 3 hours. Usual devices are used for thermoplastics such as extruders, cylinders, Banbury or Brabender mixers.
  • LOTADER A 28% n-butyl acrylate, 1% glycidyl methacrylate and the balance of ethylene and Ml 1,75 (190 ° C-2.1 6 kg) called LOTADER A. It was formulated in the following proportions:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention concerns a hot-melt adhesive with a base of a copolymer (A) comprising the following units: ethylene, optionally a monomer selected among vinyl esters or alkyl (meth) acrylate, at least an unsaturate epoxy. It can be formularized with a tackifying resin and a wax. Ethylene copolymers, n-butyl acrylate and glycidyl methacrylate are advantageously used.

Description

COLLES THERMOFUSIBLES A BASE DE COPOLYMERES A FONCTIONS HOT-MELT ADHESIVES BASED ON FUNCTIONAL COPOLYMERS
EPOXYDESEPOXIDES
La présente invention concerne une colle thermofusible à base de copolymères à fonctions époxydes et plus particulièrement celles à base de copolymère de l'éthylène et d'un monomère à fonction époxyde, ce monomère pouvant être greffé ou copolymérisé.The present invention relates to a hot-melt adhesive based on copolymers with epoxy functions and more particularly those based on a copolymer of ethylene and of a monomer with an epoxy function, this monomer being capable of being grafted or copolymerized.
Les colles thermofusibies sont des matériaux thermoplastiques solides à la température ambiante et qui par chauffage deviennent des liquides visqueux. Ces liquides visqueux sont appliqués sur un premier substrat puis on le couvre avec une seconde surface. Par refroidissement, on obtient une adhérence entre le substrat et la deuxième surface. Le temps ouvert est le temps pendant lequel la colle qui a été appliquée sur un substrat qui est à la température ambiante reste collante, c'est-à-dire pendant lequel on peut appliquer la seconde surface et par refroidissement obtenir une adhérence entre le substrat et la seconde surface.Hot melt adhesives are thermoplastic materials which are solid at room temperature and which, on heating, become viscous liquids. These viscous liquids are applied to a first substrate and then covered with a second surface. By cooling, an adhesion is obtained between the substrate and the second surface. The open time is the time during which the adhesive which has been applied to a substrate which is at room temperature remains tacky, that is to say during which the second surface can be applied and by cooling obtaining adhesion between the substrate and the second surface.
Passé le délai du temps ouvert on ne peut plus obtenir une adhérence suffisante entre le substrat et la seconde surface.After the open time has elapsed, it is no longer possible to obtain sufficient adhesion between the substrate and the second surface.
Le temps de prise est le temps nécessaire pour que l'adhérence entre le substrat et la seconde surface après leur jonction atteigne une valeur suffisante pour maintenir leur jonction intime.The setting time is the time necessary for the adhesion between the substrate and the second surface after their junction to reach a value sufficient to maintain their intimate junction.
L'adhérence peut encore évoluer dans le temps si la colle contient des fonctions réticulables, par exemple, des fonctions isocyanates réticulables à l'humidité ambiante. Outre l'adhérence entre le substrat et la deuxième surface qu'on peut mesurer par la force de pelage on caractérise aussi les colles thermofusibles par leur résistance au cisaillement en fonction de la température (test SAFT : SHEAR ADHESION FAILURE TEMPERATURE).The adhesion can still change over time if the adhesive contains crosslinkable functions, for example, isocyanate functions crosslinkable at ambient humidity. In addition to the adhesion between the substrate and the second surface that can be measured by the peeling force, hotmelt adhesives are also characterized by their shear strength as a function of temperature (SAFT test: SHEAR ADHESION FAILURE TEMPERATURE).
Ces adhésifs thermofusibles comportent généralement deux constituants principaux : un polymère thermoplastique - responsable des bonnes propriétés mécaniques et thermiques - et une résine tackifiante qui intervient au niveau adhésion, pégosité (tackiness) à chaud, fluidité et mouillabilité. On y ajoute le plus souvent un certain nombre d'additifs tels que cires, stabilisants, charges. Les cires (par exemple des paraffines) permettent d'ajuster la fluidité, le temps ouvert et le temps de prise. Les polymères thermoplastiques les plus utilisés sont les copolymères éthylène-acétate de vinyle (ci-après dénommés EVA), éthylène-(meth)acrylate d'alkyle, poly-α-oléfine atactique (APAO), caoutchouc thermoplastique, et autres. Les résines tackifiantes appartiennent principalement à trois grandes familles : les colophanes (et leurs dérivés), les résines terpéniques et les résines dérivées de pétrole (aliphatiques, aromatiques, et autres).These hot-melt adhesives generally have two main constituents: a thermoplastic polymer - responsible for good mechanical and thermal properties - and a tackifying resin which is involved in adhesion, hot tackiness, fluidity and wettability. A number of additives such as waxes, stabilizers, fillers are most often added thereto. Waxes (for example paraffins) make it possible to adjust the fluidity, the open time and the setting time. The most widely used thermoplastic polymers are ethylene-vinyl acetate copolymers (hereinafter called EVA), ethylene- (meth) alkyl acrylate, poly-α-atactic olefin (APAO), thermoplastic rubber, and others. Tackifying resins mainly belong to three main families: rosins (and their derivatives), terpene resins and petroleum-based resins (aliphatic, aromatic, and others).
EP 547 798, US 4 874 804 et US 5 242 980 décrivent de telles colles thermofusibles à base de copolymères éthylène-acrylate de n-butyle. EP 380 379 et EP 600767 décrivent des colles thermofusibles réticulables à l'humidité à base d'un prépolymère à fonctions isocyanates libres. US 5 242 980 décrit des colles thermofusibles réticulables à la chaleur constituées d'un mélange d'un copolymère de l'éthylène ayant des fonctions acides carboxyliques et d'un réticulant ayant au moins deux fonctions epoxydes tel que par exemple le diglycidyl ether du bisphenol A. Le réticulant doit être encapsulé pour éviter une réticulation prématurée pendant le chauffage de la colle pour l'appliquer sur le substrat. On a maintenant trouvé qu'on pouvait obtenir des colles ayant des propriétés améliorées par rapport aux colles à base de copolymères éthylène-(meth)acrylate d'alkyle en utilisant des copolymères de l'éthylène et comprenant des motifs epoxydes, en particulier pour la même température la force de pelage sur l'aluminium pour une colle à base d'un copolymère éthylène-acrylate de butyle-méthacrylate de glycidyle est supérieure à celle d'une colle à base d'un copolymère éhtylène-acrylate de butyle.EP 547,798, US 4,874,804 and US 5,242,980 describe such hot-melt adhesives based on ethylene-n-butyl acrylate copolymers. EP 380 379 and EP 600 767 describe hot-melt adhesives crosslinkable with humidity based on a prepolymer with free isocyanate functions. US 5,242,980 describes hot-melt crosslinkable adhesives consisting of a mixture of an ethylene copolymer having carboxylic acid functions and of a crosslinker having at least two epoxide functions such as for example the diglycidyl ether of bisphenol A. The crosslinker must be encapsulated to avoid premature crosslinking during the heating of the adhesive to apply it to the substrate. It has now been found that adhesives having improved properties compared to adhesives based on ethylene- (meth) acrylate copolymers can be obtained by using ethylene copolymers and comprising epoxide units, in particular for the same temperature the peel strength on aluminum for an adhesive based on an ethylene-butyl acrylate-glycidyl methacrylate copolymer is higher than that of an adhesive based on an ethylene-butyl acrylate copolymer.
La présente invention concerne une colle thermofusible à base d'un copolymère (A) comprenant des motifs :The present invention relates to a hot-melt adhesive based on a copolymer (A) comprising patterns:
- éthylène,- ethylene,
- éventuellement un monomère choisi parmi les esters vinyliques et les (meth)acryiates d'alkyle,- optionally a monomer chosen from vinyl esters and alkyl (meth) acrylates,
- au moins un époxyde insaturé. A titre d'ester vinyliques, on peut citer les esters vinyliques d'acides carboxyliques saturés ayant de 2 à 6 atomes de carbone tels que l'acétate de vinyle ou le propionate de vinyle.- at least one unsaturated epoxide. As vinyl esters, mention may be made of vinyl esters of saturated carboxylic acids having from 2 to 6 carbon atoms such as vinyl acetate or vinyl propionate.
A titre de (meth)acrylates d'alkyle, on peut citer ceux dont le groupe alkyle a de 1 à 10 atomes de carbone tels que le (meth)acrylate de méthyle, le (meth)acrylate d'éthyle, le (meth)acrylate de n-butyle, le (meth)acrylate d'isobutyle et le (meth)acrylate de 2-ethyl-hexyle. On utilise avantageusement l'acrylate de n-butyle.Mention may be made, as alkyl (meth) acrylates, of those whose alkyl group has from 1 to 10 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) n-butyl acrylate, isobutyl (meth) acrylate and 2-ethyl-hexyl (meth) acrylate. Advantageously, n-butyl acrylate is used.
Des exemples d'époxydes insaturés utilisables comme constituants du polymère (A) sont notamment : - les esters et éthers de glycidyle aliphatiques tels que l'allylglycidyléther, le vinylglycidyléther, le maléate et l'itaconate de glycidyle, l'acrylate et le méthacrylate de glycidyle, et, - les esters et éthers de glycidyle alicycliques tels que le 2-cyclohéxène- 1 -glycidyléther, le cyclohexène-4,5-diglycidylcarvboxylate, le cyclohéxène-4- glycidyl carboxylate, 5-norbornène-2-méthyl-2-glycidyl carboxylate et endocis- bicyclo(2,2, 1 )-5-heptène-2,3-diglycidyl dicarbo-xylate. L'époxyde insaturé peut être copolymérisé avec l'éthylène et l'autre monomère, ou être greffé sur le copolymère de l'éthylène et de l'autre monomère.Examples of unsaturated epoxides which can be used as constituents of polymer (A) are in particular: - aliphatic glycidyl esters and ethers such as allylglycidylether, vinylglycidylether, glycidyl maleate and itaconate, acrylate and methacrylate glycidyle, and, - alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidylether, cyclohexene-4,5-diglycidylcarvboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate and endocis - bicyclo (2,2, 1) -5-heptene-2,3-diglycidyl dicarbo-xylate. The unsaturated epoxide may be copolymerized with ethylene and the other monomer, or be grafted onto the copolymer of ethylene and the other monomer.
On utilise avantageusement le méthacrylate de glycidyle. La quantité d'époxyde insaturé peut représenter jusqu'à 10 % en poids du copolymère (A) avantageusement 0, 1 à 8 % et de préférence 0,5 à 5 % [les pourcentages et les parties dans le présent texte sont en poids sauf indication contraire].Advantageously, glycidyl methacrylate is used. The amount of unsaturated epoxide can represent up to 10% by weight of the copolymer (A) advantageously 0.1 to 8% and preferably 0.5 to 5% [the percentages and the parts in the present text are by weight except otherwise indicated].
La quantité de comonomère (ester vinylique et (meth)acrylate d'alkyle) peut représenter 0 à 50 % du copolymère (A) et de préférence 25 à 40 %. L'indice de fluidité (ou Melt Index MI) peut être quelconque pourvu qu'on puisse formuler une colle thermofusible et que la colle ainsi formulée ait une viscosité BROOKFIELD mesurée (à 170°C dans les conditions suivantes : Aiguille 27 à 10 tours/minute selon ASTM D 3236) comprise entre 1 000 et 10 000 mPa.s et de préférence entre 2 000 et 8 000. Avantageusement, il peut être compris entre 0, 1 et 1 500 de préférence entre 50 et 900 (g/10 minutes à 1 90°C sous 2.1 6 kg ASTM D 1 238) .The amount of comonomer (vinyl ester and alkyl (meth) acrylate) can represent 0 to 50% of the copolymer (A) and preferably 25 to 40%. The melt index (or Melt Index MI) can be arbitrary provided that a hot-melt adhesive can be formulated and that the adhesive thus formulated has a measured BROOKFIELD viscosity (at 170 ° C. under the following conditions: Needle 27 at 10 turns / minute according to ASTM D 3236) between 1,000 and 10,000 mPa.s and preferably between 2,000 and 8,000. Advantageously, it can be between 0, 1 and 1,500, preferably between 50 and 900 (g / 10 minutes at 190 ° C under 2.1 6 kg ASTM D 1 238).
Le point de ramollissement de (A), aussi appelé température bille- anneau, et mesuré selon la norme ASTM E28 peut être compris entre 60 et 1 10°C et avantageusement entre 70 et 90°C. Selon une forme particulière de l'invention, le copolymère (A) peut être un mélange d'un polymère (B) qui est un copolymère de l'éthylène et d'au moins un monomère choisi parmi les esters vinyliques et les (meth)acrylates d'alkyle et d'un polymère (A1 ) qui est un copolymère deThe softening point of (A), also called ball-ring temperature, and measured according to standard ASTM E28 can be between 60 and 110 ° C. and advantageously between 70 and 90 ° C. According to a particular form of the invention, the copolymer (A) can be a mixture of a polymer (B) which is a copolymer of ethylene and of at least one monomer chosen from vinyl esters and (meth) alkyl acrylates and a polymer (A1) which is a copolymer of
- l'éthylène, - d'au moins un monomère choisi parmi les esters vinyliques et les- ethylene, - at least one monomer chosen from vinyl esters and
(meth)acrylates d'alkyle,(meth) alkyl acrylates,
- d'au moins un époxyde insaturé.- at least one unsaturated epoxide.
Les esters vinyliques et les (meth)acrylates d'alkyle peuvent être choisis parmi les monomères déjà cités plus haut. Ces monomères peuvent être les mêmes dans les polymères (AU et (B) .The vinyl esters and the alkyl (meth) acrylates can be chosen from the monomers already mentioned above. These monomers can be the same in the polymers (AU and (B).
Les polymères (AU et (B) peuvent être quelconques pourvu que les teneurs en époxyde et le Ml soient avantageusement dans les plages citées pour (A). Les polymères (B) et les copolymères (A) dans lesquels l'époxyde n'est pas greffé peuvent être fabriqués par polymérisation radicalaire entre 500 et 2 800 bars en présence d'un initiateur de radicaux libres tels qu'un peroxyde. S'agissant des copolymères (A) dans lesquels l'époxyde est greffé, on peut les préparer par exemple en partant d'un copolymère de l'éthylène et d'éventuellement un monomère choisi parmi les esters vinyliques et les (meth)acrylates d'alkyle qu'on met en contact avec l'époxyde insaturé en présence d'un initiateur tel qu'un peroxyde. Ceci peut être fait à l'état fondu ou dans un solvant. Avantageusement, le copolymère (A) est un copolymère de l'éthylène, d'un (meth)acrylate d'alkyle dont le groupe alkyle a de 1 à 4 atomes de carbone et du méthacrylate de glycidyle comprenant 25 à 35 % de (meth)acrylate et 0,8 à 5 % d'époxyde et ayant un Melt Index entre 1 80 et 250. Avantageusement, le (meth)acrylate d'alkyle est l'acrylate de n-butyle. Avantageusement, les colles de l'invention peuvent en outre contenir une ou plusieurs résines tackifiantes, des cires, des plastifiants, des charges et des stabilisants.The polymers (AU and (B) may be any provided that the contents of epoxide and MI are advantageously within the ranges mentioned for (A). The polymers (B) and the copolymers (A) in which the epoxide is not grafted can be produced by radical polymerization between 500 and 2800 bars in the presence of a free radical initiator such as a peroxide. As regards the copolymers (A) in which the epoxide is grafted, they can be prepared, for example, starting from a copolymer of ethylene and optionally a monomer chosen from vinyl esters and (meth) acrylates d alkyl which is brought into contact with the unsaturated epoxide in the presence of an initiator such as a peroxide. This can be done in the molten state or in a solvent. Advantageously, the copolymer (A) is a copolymer of ethylene, of an alkyl (meth) acrylate in which the alkyl group has from 1 to 4 carbon atoms and of glycidyl methacrylate comprising 25 to 35% of (meth ) acrylate and 0.8 to 5% epoxide and having a Melt Index between 1 80 and 250. Advantageously, the alkyl (meth) acrylate is n-butyl acrylate. Advantageously, the adhesives of the invention can also contain one or more tackifying resins, waxes, plasticizers, fillers and stabilizers.
Des résines tackifiantes qui conviennent, sont par exemple la colophane, les esters de colophane, la colophane hydrogénée, les polyterpènes et dérivés, les résines de pétrole aromatiques ou aliphatiques, les résines cycliques hydrogénées. Ces résines ont typiquement une température bille anneau entre 25 °C et 1 80°C et de préférence entre 50 °C et 1 35 °C.Suitable tackifying resins are, for example, rosin, rosin esters, hydrogenated rosin, polyterpenes and derivatives, aromatic or aliphatic petroleum resins, hydrogenated cyclic resins. These resins typically have a ring bead temperature between 25 ° C and 180 ° C and preferably between 50 ° C and 135 ° C.
La quantité de résine tackifiante peut être de 50 à 1 80 parties pour 100 parties de copolymère (A) et de préférence 100 à 1 50 parties. Les cires peuvent être récupérées lors du raffinage de fractions pétrolières. Ce sont par exemple des cires consistant essentiellement en hydrocarbures paraffiniques et contenant des quantités suffisantes d'hydrocarbures, ramifiés, cycliques et aromatiques pour être beaucoup moins cristallines que des paraffines. On peut aussi utiliser des cires synthétiques telles que les cires FISCHER TROPSCH.The amount of tackifying resin can be from 50 to 180 parts per 100 parts of copolymer (A) and preferably 100 to 150 parts. The waxes can be recovered during the refining of petroleum fractions. These are, for example, waxes consisting essentially of paraffinic hydrocarbons and containing sufficient quantities of branched, cyclic and aromatic hydrocarbons to be much less crystalline than paraffins. It is also possible to use synthetic waxes such as FISCHER TROPSCH waxes.
Avantageusement, les cires de paraffines utilisées dans les colles de l'invention ont une température de fusion supérieure à 50°C et de préférence entre 60°C et 70°C.Advantageously, the paraffin waxes used in the adhesives of the invention have a melting temperature above 50 ° C and preferably between 60 ° C and 70 ° C.
La quantité de cire peut être comprise entre 30 et 80 parties pour 100 parties de copolymère (A).The amount of wax can be between 30 and 80 parts per 100 parts of copolymer (A).
Des compositions avantageuses comprennent 1 20 à 1 30 parties de résine tackifiante et 45 à 65 parties de cire pour 100 parties de copolymère (A). Les plastifiants que l'on peut utiliser dans les colles de l'invention sont par exemple des huiles minérales paraffiniques aromatiques ou naphténiques. Ils servent essentiellement à baisser la viscosité et à apporter du tack. La quantité de plastifiant peut être comprise entre 10 et 30 parties pour 100 parties de copolymère (A).Advantageous compositions include 1 20 to 1 30 parts of tackifying resin and 45 to 65 parts of wax per 100 parts of copolymer (A). The plasticizers which can be used in the adhesives of the invention are, for example, aromatic or naphthenic paraffinic mineral oils. They are essentially used to lower the viscosity and to provide tack. The amount of plasticizer can be between 10 and 30 parts per 100 parts of copolymer (A).
A titre d'exemples de charges, on peut citer la silice, l'alumine, le verre, les billes de verre, les carbonates de calcium, les fibres, et hydroxydes métalliques. Ces charges ne doivent pas réduire le tack ni les propriétés mécaniques de la colle après son application. La quantité de charges peut représenter jusqu'à 100 parties pour 100 parties de copolymère (A) .Mention may be made, as examples of fillers, of silica, alumina, glass, glass beads, calcium carbonates, fibers and metal hydroxides. These fillers must not reduce the tack or the mechanical properties of the adhesive after its application. The quantity of fillers can represent up to 100 parts per 100 parts of copolymer (A).
Il est recommandé d'ajouter des stabilisants tels que les antioxydants, on peut utiliser les antioxydants habituels des thermoplastiques.It is recommended to add stabilizers such as antioxidants, we can use the usual antioxidants of thermoplastics.
La température bille anneau des colles de l'invention est avantageusement comprise entre 50°C et 100°C et de préférence 60°C et 80°C.The ring bead temperature of the adhesives of the invention is advantageously between 50 ° C and 100 ° C and preferably 60 ° C and 80 ° C.
Avantageusement, le point de trouble des colles de l'invention est inférieur à 1 80°C et avantageusement inférieur à 65 °C.Advantageously, the cloud point of the adhesives of the invention is less than 180 ° C. and advantageously less than 65 ° C.
Le point de trouble est déterminé comme suit : on chauffe la colle à 175°C et on en dépose une goutte sur le bulbe d'un thermomètre ASTM puis on note la température à laquelle le trouble apparaît au cours du refroidissement. Un point trouble élevé signifie une colle constituée d'ingrédients peu compatibles et qui a donc tendance à se séparer en plusieurs phases au cours des différents cycles de chauffage et refroidissement pendant son application. Les colles thermofusibles de l'invention sont préparées par mélange à l'état fondu à des températures entre 130°C et 200°C jusqu'à ce qu'on obtienne un mélange homogène. La durée de mélange peut être de l'ordre de 30 minutes à 3 heures. On utilise les dispositifs habituels des thermoplastiques tels que des extrudeuses, des cylindres, des mélangeurs Banbury ou Brabender. Le test SAFT (ASTM D4498) est un test mesurant la température maximale supportée par un joint collé sous une charge donnée. On opère de la façon suivante : on dépose à 1 30°C à l'extrémité d'une éprouvette un carton de largeur 25 mm, deux cordons d'adhésif de diamètre approximatif 1 mm distants l'un de l'autre de 1 5 mm environ. On applique immédiatement une seconde éprouvette identique à la première et on laisse refroidir l'assemblage collé ainsi obtenu. La surface de collage ainsi obtenue est d'environ 2,5 x 2,5 = 6,25 cm2. L'assemblage collé est ensuite suspendu verticalement dans une étuve, chargé avec une masse de 500 g puis soumis à une montée en température de 25 °C à 200°C à la vitesse de 0,4°C/mn. La tenue SAFT est la température à laquelle l'assemblage cède. Ce test est effectué au moins 4 heures à 23 °C après le collage.The cloud point is determined as follows: the glue is heated to 175 ° C. and a drop is deposited on the bulb of an ASTM thermometer, then the temperature at which the cloud appears during cooling is noted. A high cloud point means an adhesive made up of incompatible ingredients and which therefore tends to separate into several phases during the various heating and cooling cycles during its application. The hot-melt adhesives of the invention are prepared by mixing in the molten state at temperatures between 130 ° C. and 200 ° C. until a homogeneous mixture is obtained. The mixing time can be of the order of 30 minutes to 3 hours. Usual devices are used for thermoplastics such as extruders, cylinders, Banbury or Brabender mixers. The SAFT test (ASTM D4498) is a test measuring the maximum temperature supported by a bonded joint under a given load. The procedure is as follows: a cardboard box 25 mm wide is placed at 1 30 ° C. at the end of a test tube, two strips of adhesive with an approximate diameter of 1 mm spaced from one another by 1 5 mm approx. A second test piece identical to the first is immediately applied and the bonded assembly thus obtained is allowed to cool. The bonding surface thus obtained is approximately 2.5 x 2.5 = 6.25 cm 2 . The bonded assembly is then suspended vertically in an oven, loaded with a mass of 500 g and then subjected to a rise in temperature from 25 ° C to 200 ° C at the speed of 0.4 ° C / min. SAFT resistance is the temperature at which the assembly yields. This test is carried out at least 4 hours at 23 ° C after bonding.
EXEMPLES Dans les exemples suivants, on a utilisé un copolymère (A) contenantEXAMPLES In the following examples, a copolymer (A) containing
28 % d'acrylate de n-butyle, 1 % de méthacrylate de glycidyle et le complément en éthylène et de Ml 1 75 (1 90°C-2.1 6 kg) qu'on appelle LOTADER A. On l'a formulé dans les proportions suivantes :28% n-butyl acrylate, 1% glycidyl methacrylate and the balance of ethylene and Ml 1,75 (190 ° C-2.1 6 kg) called LOTADER A. It was formulated in the following proportions:
35 parties LOTADER A, ELF ATOCHEM, 45 parties FORAL-AX, Colophane totalement hydrogénée de35 parts LOTADER A, ELF ATOCHEM, 45 parts FORAL-AX, Rosin completely hydrogenated
HERCULES,HERCULES,
20 parties de paraffine de type Point de fusion 68/70°C auxquelles on a ajouté 0,5 ppm d'IRGANOX 1010 antioxydant de type phénolique de CIBA.20 parts of paraffin of melting point 68/70 ° C to which was added 0.5 ppm of IRGANOX 1010 antioxidant phenolic type of CIBA.
On a utilisé la colle ainsi formulée et une colle constituée du seul LOTADER A.We used the adhesive thus formulated and an adhesive consisting of the only LOTADER A.
On a aussi utilisé un copolymère (A) contenant 28 % d'acrylate de n-butyle, 5 % de méthacrylate de glycidyle et le complément en alkylene de Ml 175 que l'on appelle Lotader (B) .A copolymer (A) containing 28% n-butyl acrylate, 5% glycidyl methacrylate and the alkylene complement of M 175 which is called Lotader (B) was also used.
On a aussi, à titre de comparaison, utilisé un copolymère contenant 28 % d'acrylate de n-butyle et 72 % d'éthylène de Ml 1 66 ( 1 90°C - 2.1 6 kg) qu'on appelle LOTRYL A, on l'a formulé dans les mêmes proportions et avec les mêmes ingrédients que le LOTADER A puis on a utilisé la colle ainsi formulée et une colle constituée du seul LOTRYL A.We also used, for comparison, a copolymer containing 28% n-butyl acrylate and 72% ethylene of Ml 1 66 (1 90 ° C - 2.1 6 kg) called LOTRYL A, we formulated it in the same proportions and with the same ingredients as LOTADER A, then we used the adhesive thus formulated and an adhesive consisting of the only LOTRYL A.
Les résultats sont reportés dans le tableau 1 suivant. The results are reported in Table 1 below.

Claims

REVENDICATIONS
1. Colle thermofusible à base d'un copolymère (A) comprenant des motifs : - éthylène,1. Hot-melt adhesive based on a copolymer (A) comprising units: - ethylene,
- éventuellement un monomère choisi parmi les esters vinyliques et les (méth)acrylates d'alkyle,- optionally a monomer chosen from vinyl esters and alkyl (meth) acrylates,
- au moins un époxyde insaturé.- at least one unsaturated epoxide.
2. Colle selon la revendication 1 dans laquelle (A) est un copolymère de l'éthylène, d'un (méth)acrylate d'alkyle dont le groupe alkyle a de 1 à 4 atomes de carbone et du méthacrylate de glycidyle comprenant 25 à 35 % en poids de (meth)acrylate, 0,8 à 5 % en poids d'époxyde et ayant un Melt Index entre 180 et 250.2. Glue according to claim 1, in which (A) is a copolymer of ethylene, of an alkyl (meth) acrylate in which the alkyl group has from 1 to 4 carbon atoms and of glycidyl methacrylate comprising from 25 to 35% by weight of (meth) acrylate, 0.8 to 5% by weight of epoxy and having a Melt Index between 180 and 250.
3. Colle selon l'une des revendications précédentes comprenant en poids :3. Glue according to one of the preceding claims, comprising by weight:
- 100 parties du copolymère (A),- 100 parts of the copolymer (A),
- 50 à 180 parties d'une résine tackifiante.- 50 to 180 parts of a tackifying resin.
4. Colle selon la revendication 3 comprenant en outre en poids 30 à 80 parties d'une cire de paraffine.4. Glue according to claim 3 further comprising by weight 30 to 80 parts of a paraffin wax.
5. Colle selon l'une quelconque des revendications précédentes dans laquelle le (méth)acrylate d'alkyle est l'acrylate de n-butyle. 5. Glue according to any one of the preceding claims, in which the alkyl (meth) acrylate is n-butyl acrylate.
EP97947087A 1996-11-26 1997-11-18 Hot-melt adhesives with copolymer base having epoxy functions Withdrawn EP0879269A1 (en)

Applications Claiming Priority (3)

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FR9614452 1996-11-26
FR9614452 1996-11-26
PCT/FR1997/002077 WO1998023698A1 (en) 1996-11-26 1997-11-18 Hot-melt adhesives with copolymer base having epoxy functions

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JP2000144082A (en) * 1998-11-16 2000-05-26 Minnesota Mining & Mfg Co <3M> Thermosetting adhesive composition, adhesive and preparation of adhesive
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EP1577345A4 (en) * 2002-10-29 2007-11-14 Kaneka Corp Thickener for thermoplastic polyester resin, thermoplastic polyester resin composition containing the same, and molded object obtained therefrom
MX2007011899A (en) * 2005-04-04 2007-11-13 Du Pont Blends of ethylene acrylate copolymers with ethylene based wax for asphalt modification.
US20070023141A1 (en) * 2005-07-29 2007-02-01 Tyco Electronics Corporation Hot melt adhesive for PTFE
KR100751946B1 (en) * 2007-01-18 2007-08-27 구자은 Non-stick adhesive composition
CN102115642B (en) * 2010-12-31 2013-01-16 广州鹿山新材料股份有限公司 EVA (ethylene vinyl-acetate copolymer) adhesive film capable of simplifying packaging structure of solar battery
JP5858576B2 (en) 2011-04-21 2016-02-10 東洋ゴム工業株式会社 Hot melt adhesive sheet for laminated polishing pad and support layer with adhesive layer for laminated polishing pad
JP5893479B2 (en) 2011-04-21 2016-03-23 東洋ゴム工業株式会社 Laminated polishing pad
BR112018000965A2 (en) 2015-08-07 2018-09-18 E. I. Du Pont De Nemours And Company asphalt composition, method for preparing the composition and paving or coating material
CN116355557B (en) * 2023-03-16 2024-01-26 广东壹诺科技股份有限公司 Low-temperature hot melt adhesive and preparation method thereof

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CN1214071A (en) 1999-04-14
WO1998023698A1 (en) 1998-06-04

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